Results in Physics 12 (2019) 989–995

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Results in Physics
journal homepage: www.elsevier.com/locate/rinp

Eco-friendly synthesis of Fe3O4 nanoparticles: Evaluation of their catalytic T

activity in methylene blue degradation by kinetic adsorption models
⁎ ⁎
Álvaro de Jesús Ruíz-Baltazara, , Simón Yobanny Reyes-Lópezb, ,
María de Lourdes Mondragón-Sánchezc, Anel Ivonne Robles-Cortésc, Ramiro Pérezd
a
CONACYT-Centro de Física Aplicada y Tecnología Avanzada, Universidad Nacional Autónoma de México, Boulevard Juriquilla 3001, Santiago de Querétaro, Querétaro
C.P. 76230, Mexico
b
Instituto de Ciencias Biomédicas, Universidad Autónoma de Ciudad Juárez, Estocolmo s/n, Ciudad Juárez, Chihuahua C.P. 32300, Mexico
c
Tecnológico Nacional de México/Instituto Tecnológico de Morelia, Posgrado en Metalúrgia, Av. Tecnológico 1500, col, Lomas de Santiaguito, C.P. 58120 Morelia, MICH,
Mexico
d
Instituto de Ciencias Físicas, Universidad Nacional Autónoma de México, Av. Universidad s/n, Col. Chamilpa, Cuernavaca, MOR 62210, Mexico

A R T I C LE I N FO A B S T R A C T

Keywords: In this work the green synthesis of Fe3O4 nanoparticles by cynara cardunculus leaf extract is presented. This green
Green synthesis synthesis route offers a novel and eco-friendly alternative to obtaining of iron oxides nanoparticles. Functional
Fe3O4 nanoparticles nanoparticles with potential catalytic applications, particularly for water remediation containing organic dyes
Kinetic adsorption models were synthetized. The structural characterization of the Fe3O4 nanoparticles were carried out by scanning
Methylene blue degradation
electron microscopy (SEM), X-ray diffraction, techniques. Calculation to obtaining the crystallite size by
Williamson –Hall method were performed. Additionally, Raman spectroscopy support the Fe3O4 characteriza-
tion. Posteriorly, the Fe3O4 nanoparticles were evaluated on the methylene blue degradation. Kinetic adsorption
models were employed to establish the behavior during the methylene blue degradation process. Pseudo first
order, Pseudo second order, Intraparticle diffusion and Elovich Models were calculated based on the experi-
mental data obtained. Calculations as the correlation factor indicates the best linear fit between the theoretical
models and the experimental data obtained during the blue methylene degradation.

Introduction respectful of the environment, non-expensive and non-toxic, represents

In recent years, the development of nanomaterials has aroused
much interest due to the potential application in multiple fields such as
physics, chemistry, biomedicine, optics, electronics and catalysis,
among other [1–4]. The reason why these nanomaterials have moti-
vated several studies, is due to the remarkable properties that are ex-
hibited, such as their high thermal and electrical conductivity, their
demonstrated catalytic activity and their biocompatibility [5–8]. In this
sense, the optimization of the morphology and distribution of the size of
the materials, conditions the mentioned properties. In the specifically
case of the iron oxide nanoparticles, many synthesis methodologies as
hydrothermal, solvothermal, electrothermal and co-precipitation
method has been reported [9–12], in this methodologies, factor as the
temperature, PH, concentration of the surfactant and reducing agents.
However, this lasted mentioned are generally toxic and in general re-
present high costs to carry out the synthesis process. For this reason, the
search for the development of new alternative synthesis routes,
a nodal challenge in the development of new nanomaterials [13–17]. In
the case of the magnetite nanoparticles has been widely studied due to
their magnetic, catalytic and biocompatibility properties [18]. The iron
oxide nanoparticles have been employed as vectors for drug, magnetic
resonance imaging contrast agents, for adsorption of antibiotics and
heavy metal and degradation of organic dyes [19,20]. The degradation
of organic pollutants from water can be focused in clean energy sources
[10,21]. For this reason in nowadays the study of the catalytic prop-
erties of the oxides iron nanoparticles has attached much interest. In
this sense, this work focuses on the attention to this problem through
functional alternatives, which represent a low cost and friendly to the
environment.
Many plants extracts have been employed and reported for the
synthesis of Fe3O4 NPs, however, the proposed methodology is simple,
economic and has not been reported [22,23]. On the other hand, Cy-
nara cardunculus has multiple therapeutic and alimentary applications
due to their great quantity of antioxidants presents in this plant [24]. In

⁎
Corresponding authors.
E-mail addresses: aruizbaltazar@fata.unam.mx (Á.d.J. Ruíz-Baltazar), simon.reyes@uacj.mx (S.Y. Reyes-López).

https://doi.org/10.1016/j.rinp.2018.12.037
Received 23 October 2018; Received in revised form 4 December 2018; Accepted 8 December 2018
Available online 20 December 2018
2211-3797/ © 2018 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
Á.d.J. Ruíz-Baltazar et al. Results in Physics 12 (2019) 989–995

this sense, the abundance and particular properties of this species allow synthesis of the Fe3O4 nanoparticles. The particle size of the Fe3O4
affirming that the Cynara cardunculus take an important role on the nanoparticles is not possible to determine only by the SEM technique, in
economic development on their cultive zones [25]. For this reason, the this case, it is necessary to make measurements from the X-ray Dif-
green synthesis of the Fe3O4 nanoparticles by sustainable material as fraction pattern from which we can calculate the crystallite size using
artichoke can be considered as a functional methodology for obtaining the Scherrer equation and the Williamson-Hall (W-H) method. This
nanoparticles of iron oxides and a novel research. analysis is presented in the X-ray characterization section presented
In this work, the green synthesis route to obtain Fe3O4 nanoparticles below.
is presented. This route is based in a reduction of the iron using cynara
cardunculus leaf extract. This eco-friendly methodology offer a facile
X-ray diffraction
synthesis at low cost and non-toxic alternative to obtaining magnetic
materials. The structural and spectroscopic characterization by
Additionally, the structural characterization of the sample is fun-
Scanning Electron Microscopy (SEM), X-ray diffraction (XRD) and
damental to support the structure of the obtained nanoparticles. Fig. 2
Raman spectroscopy is presented. In terms of the properties evaluation,
shows an X-ray diffraction (XRD) pattern of the Fe3O4 NṔs. Based on the
the methylene blue degradation by the Fe3O4 nanoparticles were stu-
intensities observed in the experimental X-Ray pattern, the symmetry
died by UV–vis spectroscopy. Kinetics adsorption models were per-
associated was the structure of the Fe3O4 (Fm3m-325) according to the
formed to establish the behavior during the methylene blue degradation
JCPDF# 96-900-5813. In order to calculate the crystallite size and
process. Pseudo first order, Pseudo second order, Intraparticle diffusion
strain, The Williamson-Hall method were carried out. Table 1 describe
and Elovich Models were calculated based on the experimental data
also the needed parameters for the W-H calculations. Following, the
obtained. Calculations as the correlation factor indicates the best linear
basic principles of the Williamson-Hall method are described in general
fit between the theoretical models and the experimental data obtained
form.
during the blue methylene degradation.
Table 1 display detailed the main parameter such as the diffraction
angle and their miller index for each peak identified. This result show
Experimental procedure
plenary, that the structure obtained is magnetite, due that the main
intensities of the experimental pattern, can be indexed whit the
Bio-synthesis of Fe3O4 nanoparticles
JCPDF# 96-900-5813. In this sense we can affirm that the reduction of
the Fe ions were carried out by the reducing agents presents on the
The Fe3O4 nanostructures were synthesis starting to a mixture of
cynara cardunculus leaf extract. In order to calculate the crystallite size
ferric chloride and ferrous chloride in a 1:2 M ratio. The reducing agent
and strain, The Williamson-Hall method were carried out. Table 1 de-
employed was cynara cardunculus leaf extract with voucher specimen
scribe also the needed parameters for the W-H calculations.
number 260583. The plant was obtained from Tarímbaro City, Mex.
Following, the basic principles of the Williamson-Hall method are
Briefly, a solution of [Fe (III)/Fe (II)] in aqueous solution at 50 mM was
described in general form.
prepared in aqueous solution. On other hand, 5 gr of dried leaves of
cynara cardunculus was milled and transferred to a 50 ml flask with
30 ml of deionized water. The cynara cardunculus was heated to 100 °C Williamson-Hall analysis
for 20 min. The infusion obtained was cooled at room temperature and
mixed whit 20 ml of [Fe (III)/Fe (II)] solution (50 mM). The PH asso- The crystallite and strain can be calculated by Williamson-Hall
ciated with the reaction was adjusted to 11 through a solution of NaOH. method, in general form this methodology implies the instrumental
A color change of the post-reaction mixtures from dark brown into broadening (β) corrected for each diffraction peak by relation:
black color was observed. This coloration change indicate the iron 2
βhkl = (βhkl )2measured − (βhkl )2instrumental (1)
oxide formation.
On the other hand the Debye-Scherer’s equation can be employed to
Methylene blue degradation calculate the average nanocrystallite size, which is described following:

The catalytic activity analysis of Fe3O4 NṔs was carried out through kλ
D=
the degradation of MB. The experiments were performed employed βhkl cosθ (2)
3 mg of Fe3O4 NṔs synthesized cynara cardunculus leaf extract. The in-
Complementary, has been reported that the strain induced in
itial concentration of MB was 30 mgL−1. The MB degradation process
powders associated to the crystallite defects is calculated by:
was monitored by UV–vis in intervals of 5 min until the SPR of the
organic dye disappeared. βhkl
ε=
4 tanθ (3)
Results and discussions
In this sense, W-H method incorporate the previous equations, given
Scanning Electron Microscopy (SEM) as result an expression to calculate the crystallize size and strain (Eq.
(4)) from the broadening corrected and observed by the experimental
Fig. 1(a) shows the Fe3O4 nanoparticles obtained by green synthesis X-Ray diffraction patter of Fe3O4 NṔs.
using cynara cardunculus leaf extract. In this image we can appreciated kλ
the Scanning Electron Microscopy (SEM) obtained by detection of βhkl = + 4ε tanθ
Dcosθ (4)
secondary electrons (SE). The morphology observed is semi-spherical,
several agglomerates can be appreciated. Several studies [2,26,27] Simplifying the previous equation, we have:
describes this agglomeration as a stearic effect attributed to the inter-
kλ
action of the actives sites of the NṔs surface. However, the magnetic βhkl cosθ = + 4ε senθ
D (5)
interaction generated by the individuals Fe3O4 nanoparticles is con-
siderate to explain this agglomeration observed by SEM. In order to The above equations are known as the W-H expressions. Fig. 3 il-
establish the chemical composition of the nanoparticles, Fig. 1(b) dis- lustrate graphically, the results associated to the crystallize size and
play an EDS spectrum of the sample, the main components observed strain obtained from the Fe3O4 NṔs synthesized by green route. The
were Fe and O. Initially, the chemical composition is consistent with the crystal size calculated was 13.5 nm.

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Á.d.J. Ruíz-Baltazar et al. Results in Physics 12 (2019) 989–995

Fig. 1. (a) SEM image and (b) EDS chemical analysis of Fe3O4 nanoparticles synthesized by cynara cardunculus leaf extract.

Fig. 3. Williamson-Hall plots of the Fe3O4 nanoparticles obtained by green

Fig. 2. X-ray diffraction (XRD) pattern of the Fe3O4 NṔs synthesized by cynara
synthesis using cynara cardunculus leaf extract.
cardunculus.

expected vibrational modes of the first Brillouin zone center corre-

Raman spectroscopy
In complementary form, the Raman spectrum of the Fe3O4 nano-
particles is presented in order to support the structural characterization
by X-ray diffraction technique and identified the main phase present in
the synthesized simple. Fig. 4 shows the Raman spectrum of the na-
noparticles. Due to the magnetite possesses spinel symmetry, the
sponding to this structure are given by Eq. (6) [24]:
Γvib =A1g + E1g + T1g + 3T2g + 2A2u + 2Eu + 4T1u + 2T2u (6)
In Fig. 4, we can identify the vibrational modes corresponding to the
magnetite as principal phase. The typical vibrational mode associated
to magnetite is situated t 667 cm−1 which is the most pronunciation

Table 1
Parameters employed for the Williamson-Hall calculations.
2θ d-spacing hkl FWHM FWHM Asymmetry Areal Integral Shape Factor (observed Size (nm) Size (nm)
(Amstrongs) (observed) (corrected) asymmetry breadth FWHM/Integral uncorrected corrected
breadth)

18.44 4.807 111 0.5474 0.544 0.4924 0.833 0.521 1.052 16.3 16.4
30.24 2.9531 220 0.6196 0.6127 0.8303 0.7458 0.772 0.803 14.8 14.9
35.62 2.5185 311 0.6083 0.5987 0.7082 0.7273 0.764 0.797 15.2 15.5
37.1 2.4213 222 0.6038 0.5932 1.2275 1.0472 0.439 1.375 15.4 15.7
43.22 2.0916 400 0.645 0.6312 0.93 1.6239 0.193 3.346 14.7 15
53.68 1.7061 422 0.7675 0.7485 0.7547 0.5042 0.634 1.12 12.9 13.2
57.16 1.6102 511 0.7687 0.7466 0.7964 0.9468 0.821 0.936 13.1 13.5
62.72 1.4802 440 0.767 0.7386 1.1993 1.0458 0.884 0.868 13.5 14
64.06 1.4524 531 0.1186 0.1186 2.7933 1.7203 0.163 0.728 87.8 87.8
71.08 1.3252 620 0.4952 0.4203 1.351 1.8582 0.331 1.498 21.9 25.8
74.14 1.2779 533 1.1959 1.1689 0.8996 0.866 1.874 1.847 9.3 9.5
77.26 1.2339 444 0.4839 0.3833 0.2629 0.408 0.398 1.217 23.3 29.5

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Á.d.J. Ruíz-Baltazar et al.
Fig. 4. Raman spectrum of the Fe3O4 NPs synthesized by cynara cardunculus
leaf extract.
peak and correlated to the A1g mode. The peaks located at 302 and
545 cm−1 are also representatives of the Magnetite and attributed to
the T1g vibrational mode [28].
Additionally, the band associated to the magnetite and hematite
phases are corroborated whit Raman spectra obtained from the RRUFF
Raman Mineral Spectra data base (University of Arizona). This Raman
spectrum (Fig. 5a and b) indicates clearly the bans associated to the
magnetite and hematite phases. Is important to note that the magnetite
and hematite phases are presents in the experimental Raman spectrum,
however, the majority phase observed is the magnetite. On the other
hand, both phases are very similar from the point of view of the
structure and the facile formation of both phases during the synthesis
process is very common due to the facile interaction between the col-
loidal media and the iron oxide surface, promoting the oxidation of the
samples. Nerveless, the green synthesis process offer a great route to
obtaining magnetite NṔS as majority phase, taking a count that there is
not used any surfactant agent and the reducing agent employed (cynara
cardunculus leaf extract) can be act in controlled form in comparison
whit another reducing agents as for example the sodium borohydride
(NaBH4), which is more active in their reducing capacity and toxic
[29,30]. In this sense, dispense with a surfactant agent during the green
synthesis process presented, favors the reduction of the ionic iron with a
suitable reaction speed for the gradual formation of iron oxide phases.
Giving as a result a green and functional methodology for obtaining
magnetite.
In order to elucidate the organic compound presents on the cynara
Fig. 5. Raman spectra referenced to the (a) Magnetite and (b) Hematite phases.
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Results in Physics 12 (2019) 989–995
cardunculus leaf extract, Fig. 6(a) shows the UV–vis spectrum of the
cynara cardunculus extract. In this image we can appreciate the typical
SPR of the flavonoids, which are identified by two mains bands. The
band (I) is associated to the flavonols with the hydroxyl group in the
ring C3 (insert Fig. 6a) [24]. Has been reported that the typical flavonol
presents in the Cynara cardunculus is the quercetin. On the other hand,
the band (II) is associated to the flavones. The mentioned compounds
are also identified in the cynara cardunculus as the catechine among
others [31]. Has been widely reported that the flavonoids exhibits a
great antioxidant activity and consequently, the hydroxyl groups can
favors the reduction of the iron ions given as results the magnetite
formation [25]. In order to support the results obtained by UV–vis,
Fig. 6(b) describe the FT-IR spectrum of the cynara cardunculus extract.
Intensities located at 3306 cm−1 is attributed to the C-H stretching vi-
brations in the CH2 groups identified on the aliphatic compound [25].
The bands at 1585 and 1398 and 1268 cm−1 are associated to the
aromatics compounds such as polysaccharides [24,25]. Finally, the
band observed at 1094 cm−1 can be associated to the aliphatic amines
presents in the flavonoids identified by UV–vis spectroscopy. In this
sense, the fully identifications of the organic species such as the fla-
vonoid in the cynara cardunculus extract by UV–vis spectroscopy, al-
lows to affirm that specifically the flavones and flavonols observed are
responsible directly of the Fe ions reduction and consequently to the
Fe3O4 NPs formation.
Theoretical adsorption kinetic models
The adsorption rate of MB observed was evaluated in terms of the
four theoretical adsorption models, Pseudo first order, Pseudo second
order, Elovich and intraparticle diffusion model. The first two models
are expressed by Eqs. (7) and (8) [32].
dq
= K1 (qe − qt )
dt (7)
dq
= K2 (qe − qt )2
dt (8)
where K1 (min−1) and K2 (g mg−1 min−1) are the adsorption rate
constants for pseudo first order and pseudo second order, respectively.
Also, qt and qe represent the adsorption capacity at time t and in the
equilibrium, respectively [33,34].
On the other hand, the Elovich or Roginsky and Zeldovich equation
would be:
dqt
= αe−βqt
dt (9)
Additionally, Intraparticle Diffusion Model was employed to eluci-
date the MB diffusion mechanism. The kinetic equation that governs
this model is [35,36]:
Á.d.J. Ruíz-Baltazar et al. Results in Physics 12 (2019) 989–995

Fig. 6. (a) UV–Vis and (b) FT-IR spectra of the cynara cardunculus leaf extract employed for the green synthesis of the Fe3O4NPs.

In order to validate the MB concentration, a calibration curve of

Fig. 7. Calibration curve for methylene blue absorbance in a range of
5–50 mgL−1. (For interpretation of the references to color in this figure legend,
the reader is referred to the web version of this article.)
qt = ki t + Ci
different concentration of MB solutions (5–50 g mL−1) was obtained
(Fig. 7). The R2 factor observed in this linear fit is 0.9753 which can be
accurate for the subsequent measurements.
Fig. 8 (a) shows the UV–vis spectrum associated to the Fe3O4 NṔS,
MB and Fe3O4/MB at time t = 0. In this imagen we can appreciate the
typical intensity at 658 nm corresponding to the n–π* transition of MB
[37]. However, the UV–Vis spectrum of the Fe3O4 NṔs, only exhibits a
low intensity at 230 nm, which can be associated to the organic com-
pounds, which are derivate of the green synthesis of the Fe3O4 NṔS. In
this sense, Fig. 8(b) shows clearly the MB degradation by the Fe3O4 NṔS
in a range of time of 80 min. The typical absorption band associated to
the MB has been diminished and finally it disappeared after 80 min of
reaction, which indicates that the degradation of Methylene blue dye
occurs [14].
In order to evaluate the kinetic adsorption model that describes in
best form the MB degradation process, Fig. 9(a)–(d) illustrate the
Pseudo first and second order model, the intraparticle diffusion and
Elovich model, respectively.
Based on the experimental data obtained, the linear fit of the data
were obtained. The correlation factor R2 calculated from each kinetic
model, determinate the best approximation between the experimental
(10) data and the theoretical models. Table 2 indicate the kinetic parameter

Fig. 8. (a) UV–vis spectrum of the initial samples Fe3O4, Fe3O4-MB and MB (30 mgL−1), (b) Methylene blue degradation by Fe3O4 nanoparticles obtained by green
synthesis route.

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Á.d.J. Ruíz-Baltazar et al. Results in Physics 12 (2019) 989–995

Fig. 9. Kinetic adsorption models (a) Pseudo-first order, (b) Pseudo second order model, (c) Elovich and (d) intraparticle diffusion model.

Table 2 and with homogeneous particle sizes. Is important to note that the
Kinetic parameter calculated from Pseudo first and second order model, the particles obtained exhibits a great stability and the agglomerates for-
intraparticle diffusion and Elovich model. mation is not observed. Additionally, the kinetic adsorption parameter
Model Kinetic parameter calculated during the MB degradation process, indicate a competitive
behavior respect to the catalytic properties reported for the Fe3O4
Lagergren first-order K1 (min−1) K1 3.63120919 nanoparticles [37,38].
R2 0.90796

Pseudo-second order [K2] (g·mg−1·min−1) qe (mg·g−1) K2 0.00617457

H2 0.00126455
Conclusions
qe 0.45254807
R2 0.96435 The synthesis of Fe3O4 NṔs by cynara cardunculus was carried out.
Intraparticle Duffusion Ki (mg·g−1·min−0.5) Ci 0.03256 The antioxidant properties associated to the cynara cardunculus have
Ki 0.01557 the capacity to reduce the iron ions presents in the precursor solution.
R2 0.88554 Additionally, the PH control of during the synthesis process take also a
Elovich α (mg·g−1·min) β (g·mg−1) α 2.40962738 fundamental role in the iron reduction process. The magnetite structure
β 0.04733 was fully identified by X-ray diffraction technique and Raman spec-
R2 0.79083 troscopy. We can conclude that the synthesis conditions were adequate
for the Fe3O4 NṔs obtaining. However, the green synthesis by cynara
cardunculus leaf extract offers an eco-friendly and non-toxic alternative
calculate for the four models and their respective correlation factor R2.
to obtaining Fe3O4 NṔs. On the other hand, the Fe3O4 NṔs obtained
In this sense, the Pseudo-second order model exhibits the highest value
shows a catalytic activity in the methylene blue degradation process.
of R2 (0.975). This value suggests that the MB degradation process
The MB degradation rate and the kinetic adsorption behavior is gov-
follows a kinetic adsorption model of Pseudo second order.
erned by the Pseudo- second order model (type 2) which describe an
In this regard, several reports indicate that the exchange ionic and
exchange ionic and chemisorption process between the positive partial
chemisorption process are associated to the pseudo-second order model
charges of the Fe3O4 NṔs and the molecule of the MB. Given has result
[2]. In this sense, it is possible that the positive partial charges of the
the decomposition of the MB molecule and consequently the MB de-
Fe3O4 can interact with the molecule of the MB. The particle size of the
gradation. Finally, we can affirm that the Fe3O4 NṔs synthetized by
nanoparticle plays a significant role in the degradation process due that
cynara cardunculus leaf extract have potential catalytic applications,
the smaller particles sizes promotes a larger potential difference be-
particularly for water remediation containing this kind of organic dyes.
tween Fe3O4 NṔs and MB and hence a higher catalytic activity.
In comparison with other methodologies to obtaining of Fe3O4 by
green routes, the use of cynara cardunculus offer an efficient green Conflict of interest
route to obtaining Fe3O4 nanoparticles with high crystallinity degree
On behalf of all authors, the corresponding author states that there

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Á.d.J. Ruíz-Baltazar et al. Results in Physics 12 (2019) 989–995

is no conflict of interest. synthesis of silver nanoparticles using a Melissa officinalis leaf extract with anti-
bacterial properties. Results Phys 2017;7. https://doi.org/10.1016/j.rinp.2017.07.
044.
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